Heavy Metal Separation from Flue Gas Scrub Water with TMT15 McIlvaine Company Hot Topic Hour on FGD Wastewater Treatment Rüdiger Peldszus June 16, 2011
An attractive company One of the global leaders in its core specialty chemicals business Investments in the energy and real estate sectors Sales 2010 Chemicals Real Estate EBITDA Profitability (EBITDA margin) Return on capital employed (ROCE) Employees 2010 13.3 billion 12.9 billion 0.4 billion 2.365 billion 17.8% 15.0% 34,407 6/10/2011 AI-AK-SK-AT/Peldszus /TMT - McIlvaine Hot Topic Hour - 2011-06-16.ppt Page 2
Trimercapto-s-triazine Representative Product: Application: Industries: TMT 15, Evonik Industries AG Heavy metal precipitation agent - Combustion/Incineration Plants - Metalworking/Chemical Industry - Mining Structure: NaS C N C SNa N C N SNa Product Data: CAS- No.: 17766-26-6 Commodity: aqueous solution Appearance: light yellow liquid (MSDS Evonik Degussa GmbH) Odor: almost odorless (MSDS Evonik Degussa GmbH) 10.06.2011 AI-AK-SK-AT/Peldszus /TMT - McIlvaine Hot Topic Hour - 2011-06-16.ppt Seite 3
Reaction of TMT 15 with Heavy Metals (e. g. Mercury) 3 Hg 2+ + 2 TMT 3- = Hg 3 TMT 2 = TMT 15 (C 3 S 3 N 3 Na 3 ) = Heavy Metal e. g. Hg 2+ 10.06.2011 AI-AK-SK-AT/Peldszus /TMT - McIlvaine Hot Topic Hour - 2011-06-16.ppt Seite 4
Waste Water Treatment Neutralization fails in the presence of Complexes Alternative Process: Precipitation with TMT 15
TMT 15 Application in Combustion Plants Coal/garbage contains heavy metals which are set free during combustion Main problem: Toxic Mercury and Cadmium Elimination of toxic heavy metal out of flue gas scrub water by precipitation Evonik s proven application in several hundred combustion plants worldwide Minimization of mercury emission in flue gas 10.06.2011 AI-AK-SK-AT/Peldszus /TMT - McIlvaine Hot Topic Hour - 2011-06-16.ppt Seite 6
TMT 15 at Coal Fired Power Stations - Flue gas wash water treatment Typical treatment: Neutralisation to ph 9 Hydroxide precipitation Addition of TMT 15 Mercury precipitation Flocculation with Polyelectrolyte (sometimes additional ferric dosage to optimize the flocculation) Particle removal by circular or lamellar clarifier Fine particle removal e.g. by sand filter Additional treatment like biological processes possible FGWW * Neutralization Lime/ caustic TMT 15 Hg pptn. with TMT 15 Filtrate Flocc. Flocculation Filter press Sedimentation Sand filter Receiving water * FGWW = Flue Gas Wash Water 10.06.2011 AI-AK-SK-AT/Peldszus /TMT - McIlvaine Hot Topic Hour - 2011-06-16.ppt Seite 7
Flue Gas Scrub Water treatment - Coal fired power station Treatment Conditions : Several 0.25 l samples of neutral flue gas scrub water (ph = 5.6) set to ph 9 with NaOH, different quantities of TMT15 added (30 minutes reaction time), flocculated (Polyelectrolyte, approx. 3 ml 0.1%sol./l), after 1.5 h sedimentation time filtered by a 0.2 membrane filter and the residual concentration of heavy metals analyzed by ICP * 47. German administrative fiat 10.06.2011 AI-AK-SK-AT/Peldszus /TMT - McIlvaine Hot Topic Hour - 2011-06-16.ppt Seite 8
TMT 15 at Coal Fired Power Stations - Hard Facts / Instance plant I CFP Station, Germany Total 580 MW (2 blocks) German + Import Hard Coal (Summer ~125 t/h : Winter ~190 t/h) Wet FGD system with wash water treatment Blowdown: TMT 15 Addition: 15-20 m³/h flue gas scrub water 20 ml TMT 15 /m³ blowdown = 2.5 ml TMT 15 /t coal Residual mercury content: < 0.2 µg Hg/l Residual cadmium content: < 0.2 µg Cd/l TMT 15 application since FGD start up in 1988 CFP = Coal fired power station 10.06.2011 AI-AK-SK-AT/Peldszus /TMT - McIlvaine Hot Topic Hour - 2011-06-16.ppt Seite 9
TMT 15 at Coal Fired Power Stations - Hard Facts / Instance plant II CFP Station, Germany, 356 MW Import Hard Coal, 120 t/h SCR + wet limestone FGD system with wash water treatment CFP = Coal fired power station Blowdown: TMT 15 Addition: 20 m³/h flue gas scrub water 50 ml TMT 15 /m³ blowdown = 8 ml TMT 15 /t coal Residual mercury content: < 1 µg Hg/l TMT 15 application since FGD start up in 1989 10.06.2011 AI-AK-SK-AT/Peldszus /TMT - McIlvaine Hot Topic Hour - 2011-06-16.ppt Seite 10
Heavy Metal Separation with TMT 15 Classification Toxicity Handling Safety Benefits
TMT 15 Classification / Toxicity Classification Toxicity CAS-RN 17766-26-2 Acute tox. 7 878 LD 50 * (rat, mg/kg) Commodity 15% solution Lethal conc. LC 0 ** (fish, mg/l) 12 000 GHS-Labelling Mutagenity no Warning Transportregulations No dangerous good 10.06.2011 AI-AK-SK-AT/Peldszus /TMT - McIlvaine Hot Topic Hour - 2011-06-16.ppt Products of decomposition none * LD50 = Concentration where 50% of the rats die ** LC0 = Concentration where no fish dies Seite 12
Best Available Techniques (BAT) for Waste incineration http://eippcb.jrc.es Abstract of: WI_BREF_FINAL / Chapter 5.1 Generic BAT for all waste incineration 10.06.2011 AI-AK-SK-AT/Peldszus /TMT - McIlvaine Hot Topic Hour - 2011-06-16.ppt Seite 13
Best Available Techniques (BAT) for Waste incineration http://eippcb.jrc.es Abstract of: WI_BREF_FINAL Chapter 3.3.5 Hazardous waste incineration plants European survey data - Mercury 10.06.2011 AI-AK-SK-AT/Peldszus /TMT - McIlvaine Hot Topic Hour - 2011-06-16.ppt Seite 14
TMT 15 at Coal Fired Power Stations TMT 15 : Proven application in several hundred combustion plants worldwide thereof 135 coal fired power stations Residual mercury concentration in treated flue gas wash water in the range of a few µg Hg/l or less can be reached based on precipitation with TMT 15 and a subsequent efficient removal of the precipitate Trimercaptotriazine (TMT) is announced from the European Commission as Best Available Techniques (BAT) for waste incineration where wet flue-gas treatment is used too 10.06.2011 AI-AK-SK-AT/Peldszus /TMT - McIlvaine Hot Topic Hour - 2011-06-16.ppt Seite 15
Heavy metal precipitation Benefits of TMT 15 highly effective in various applications proven application and state-of-the-art in combustion plants stable heavy metal compounds non-toxic and non-hazardous safe handling and no unpleasant odor good ecological properties qualified and up to date support experienced application and technical competence 10.06.2011 AI-AK-SK-AT/Peldszus /TMT - McIlvaine Hot Topic Hour - 2011-06-16.ppt Seite 16
Information / Contact TMT 15 Homepage www.evonik.com/tmt15 Application and Technology Ruediger Peldszus Senior Manager Applied Technology Evonik Degussa GmbH 63457 Hanau-Wolfgang Germany Phone +49 6181 59-2854 E-Mail: ruediger.peldszus@evonik.com Region: North America Joe Lally Technical Development Manager Evonik Degussa Corporation 17211 Camberwell Green Lane Houston, Texas 77070 USA Phone +1 832 717 0927 Mobile +1 732 259 7150 E-Mail: joe.lally@evonik.com 10.06.2011 AI-AK-SK-AT/Peldszus /TMT - McIlvaine Hot Topic Hour - 2011-06-16.ppt Seite 17